Dyeing keratinous fibers with dye compositions containing indoanilines

ABSTRACT

A dye composition for keratinous fibers and in particular, human hair comprises an aqueous solution of an indoaniline having the formula

United States Patent [191 Kalopissis et al.

14 1 Feb. 18, 1975 [22] Filed: Dec. 29, 1971 [21] Appl. No.: 213,750

[30] Foreign Application Priority Data Dec. 30, 1970 Luxembourg 62348 [52] U.S. Cl 8/10, 8/10.1, 8/102, 8/11, 260/247.5 R, 260/2477 A, 260/396 N, 260/562 R, 260/575, 424/D1G. 1, 424/DlG.

Primary Examiner-Jerome D. Goldberg Assistant ExaminerVera C. Clarke Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT A dye composition for keratinous fibers and in particular, human hair comprises an aqueous solution of an indoaniline having the formula wherein R R R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-6 carbon atoms and halogen with the proviso that 1 2 of R R R and R are other than hydrogen; R R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 16 carbon atoms and lower .alkoxy having 1-6 carbon atoms; R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-6 carbon atoms; R represents a member selected from the group consisting of hydrogen and lower alkyl having 16 carbon atoms and together with R and the nitrogen atom to which R is attached form dihydrooxazine; and Z represents a member selected from the group consisting of amino, acetylamino and hydroxy; the hydrochloride of said indoaniline and a double chloride of zinc and said indoaniline. The indoaniline is present in amounts of 0.002 2 percent by weight of said composition.

8 Claims, No Drawings DYEING KERATINOUS FIBERS WITH DYE COMPOSITIONS CONTAINING INDOANILINES The present invention relates to novel indoanilines having the formula wherein R R R and R each independently represents a member selected from the group consisting of hydrogen, lower alkyl having 1 6 carbon atoms and halogen such as chlorine and bromine with the proviso that l 2 of R R R and R are other than hydrogen; R R and R each independently represent a member selected from the group consisting of lower alkyl having 1 6 carbon atoms and lower alkoxy having 1 6 carbon atoms; R represents a member selected from the group consisting of hydrogen, lower alkyl having I 6 carbon atoms, lower alkyl having I 6 carbon atoms and substituted with a member selected from the group consisting of amino, hydroxyl, carbamoyl, piperidinyl and acylamino and together with R and the nitrogen atom to which R is attached form a heterocycle selected from the group consisting of dihydrooxazine and pyrroline; R represents a member selected from the group consisting of hydrogen, lower alkyl having 1 6 carbon atoms, lower alkyl having 1 6 carbon atoms and substituted with a member se' lected from the group consisting of amino, hydroxyl, carbamoyl, piperidinyl and acylamino, and together with R and the nitrogen atom to which R, is attached form a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; Z represents a member selected from the group consisting of an amino, acylamino and hydroxy; and the salts formed by these indoanilines with organic or inorganic acids, and the dou' ble zinc salts of these compounds, which can, of course, be in a tautomeric form of that represented by formula I.

The organic or inorganic acid salts of the compounds of formula l can be acetates, oxalates, hydrochlorides, hydrobromides, persulfates or perchlorates.

The indoanilines or indoaniline salts of formula I can be prepared by four different processes described below.

Method 1 A first process of obtaining the indoanilines of formula l or their salts comprises reacting a paraaminophenol having the formula:

H rr (II) (III) wherein R R R R R and Z have the meaning above, or alternatively with a salt of such a compound, for example, the dihydrochloride, dihydrobromide or sulfate thereof.

The reaction can be performed in an aqueous medium, an aqueous alcoholic medium or an aqueous acetonic medium, at a pH made alkaline by addition to said chosen medium of an aqueous solution of sodium, potassium or ammonium hydroxide, the pH preferably ranging from about 8 to 10 at a temperature between 5C and 40C and in the presence of an oxidizing agent such as air, hydrogen peroxide, ammonium persulfate or potassium ferricyanide. The indoaniline of formula I is then isolated in the form of a free base. When an aqueous alcoholic medium is employed the alcohol can be present in amounts of about 20 to 50 percent by weight of said medium and the alcohol employed is generally a lower alkanol having 1 4 carbon atoms.

When an aqueous acetonic medium is employed, ac etone can comprise between about l0 to 30 weight percent of the medium.

The amount of oxidizing agent used can vary be tween about one to five times the stoichiometric quantity for oxidizing the paraaminophenol to the corresponding quinone-imine. This amount is preferably 1-3 moles of persulphate or 2-5 moles of ferricyanide for 1 mole of paraaminophenol.

The reaction can also be performed in an aqueous medium between 0 and 20C at an acid pH, preferably ranging from about 1 to 5, and in the presence of a ferric chloride solution present in amounts of about 2 to 6 moles per mole of paraaminophenol. The indoaniline of formula I is then isolated in the hydrochloride form.

Representative paraaminophenols of formula II that can be used in accordance with the present invention are, 3-methyl-4-amino phenol, 7.,5-dimethyl-4-amino phenol, 3,5-dimethyl-4-amino phenol, 2,3-dimethyl-4- amino phenol, 2-rnethyl-4-amino phenol, 2,6-dimethyl- 4-amino phenol, 2,6-di-tert -butyl-4-amino phenol, 2- chloro-4-amino phenol and 3-cchloro-4amino phenol.

Compounds representative of those of formula lll include metaphenylenediamine, metatoluylenediamine, 2,4-diamino anisole, 3,5-diamino toluene, 1,3- dimethyl-2,4-diamino benzene, N,N-dimethyl metaphenylenediamine, 6-hydroxy phenomorpholine, 6- hydroxy-4-methyl phenomorpholine, 3-acetylamino N,N-dimethylaniline, 2-methyl-5-acetylaminoaniline, 6-amino phenomorpholine, and l-ethyl-6-amino indoline.

Generally, the paraaminophenol represented by formula II and the compound represented by formula III are employed in essentially equirnolar amounts.

Method 2 The indoanilines of formula I can also be prepared by condensation of a benzoquinenemonoimine having formula cm (v) wherein R R R and R have the meaning given above, on compound of formula [I], this condensation being performed in an aqueous medium, an aqueous alcoholic medium or an aqueous acetonic medium, also as defined above, at a temperature between and 40C.

Representative quinone-chloroimides that can be used include, for example, 3-methyl quinone chloroimide, 2-chloro quinone chloroimide, 3-chloro quinone chloroimide, 2,5-dimethyl quinone chloroimide, 2,3- dimethyl quinone chloroimide and 3,5-dimethy] quinone chloroimide. Essentially equimolar amounts of the quinone-chloroimide and compound III are employed.

Method 4 The indoanilines of formula lean also be prepared by reacting a nitroso derivative having the formula OH- --OH wherein R R R and R, have the meaning above, with a compound of formula Ill. The condensation reaction is performed in an alcohol medium in the presence of zinc chloride at the reflux temperature of the reaction medium. The indoaniline is then isolated in the form of double zinc salt. The alcohol used for the reaction medium can be a lower alkanol having l 4 carbon atoms and the zinc chloride is generally present in amounts sufficient for precipitating the product.

The indoanilines according to the present invention and their salts constitute dyes which present good dyeing power with regard to keratinous fibers and, in particular, human hair, this in a pH range varying from 4 to 11. Because of their great affinity for these fibers they can be used at very slight concentrations, for instance, from about 0.002 to 0.005% by weight of the dye composition, which explains why even salts that are only slightly soluble in water can be effectively used.

The indoanilines of the present invention make it possible to obtain a very wide range of shades, in particular violets, blues, greens, roses, silver grays and ash blonds which present exceptional qualities of brilliance and richness in glints. After dyeing, the hair presents a pearly and iridescent appearance.

Consequently, the present invention also provides a novel dying composition for keratinous fibers, in particular human hair, characterized by the fact that it contains in solution at least a compound of formula I or a salt of this compound.

The dye compositions according to the invention can contain only the compounds of formula I, in which case they make it possible to obtain the entire range of shades, with the exception of the yellows, and with application times that can be extremely short, of the order of 3 minutes at ambient temperature, because of the great affinity of the indoanilines of formula I with regard to keratinous fibers.

The compositions according to the invention can also contain other direct dyes, for example, anthraquinone dyes, nitro dyes of the benzene series, indamines, indophenols, oxazines, azines or indoanilines other than those of formula l.

Because of the great dyeing power of the novel compounds of formula 1, their concentration in the compositions according to the invention can, as has been said above, be extremely slight, of the order of 0.002% by weight. However, this concentration can vary from 0.002 to 2% and preferably between about 0.005 and 0.5% by weight.

The dye compositions according to the present invention are in the form of aqueous solutions, to which most often have been added low molecular weight alcohols such as ethanol or isopropanol, or glycols such as propyleneglycol or butyglycol, the alcohol or glycol facilitating the solution of the dye in the composition. The proportion of alcohol used is generally between 20 and by weight, while the proportion of glycol is generally between 1 and 6% by weight.

The compositions according to the invention can also contain various ingredients usually used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes. They can also be packaged under pressure in aerosol bombs or containers, together with a conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures. Obviously other conventional aerosol propellants can be used.

The pH of the dye compositions according to the invention can vary between 4 and l l. Preferably, however, the pH ranges between 5 and 9. To regulate this pH at a desired value, it is possible to use as alkalizing agents ammonia or an amine such as monoor dior triethanolamine and as acidifying agents, acetic acid or lactic acid.

Dyeing of keratinous fibers, in particular, human ,hair, with the dye compositions according to the invention, can be performed in the usual way, by application of the composition to the fibers to be dyed, the composition being left in contact with the fibers for a time varying from 3 to 30 minutes. Following this application, the fibers are rinsed and, if desired, washed. Thereafter, the thus treated fibers are dried.

In another embodiment of the present invention, the novel indoanilines can be employed in the production of capillary hair-setting lotions. These lotions comprise an aqueous alcohol solution, at least one cosmetic resin and at least one indoaniline of formula I or a salt thereof. The amount of indoaniline or its salt present in the hair-setting lotion according to this invention can be extremely slight. Such an amount generally varies between 0.002 and 1% by weight and preferably between 0.002 and 0.5% by weight, of the total hairsetting lotion composition, the pH of which generally lies between 5 8.

Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention include, for instance, polyvinylpyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer vinylpyrrolidone and vinyl acetate, wherein the ratio of VP to VA ranges between 50 70: 50 30, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydride butylvinyl ether copolymers, a 1% solution of which in methylethyl ketone has a viscosity of O.13.5 cps at 25C. These resins are used in a proportion of 1 to 3% by weight of the hair-setting lotion composition.

The alcohols suitable for the preparation of the hairsetting lotions according to the invention are low molecular weight alkanols, such as ethanol or isopropanol which are present in amounts of about to 70% by weight of the total hair-setting lotion composition.

The setting lotion of the present invention can contain only the indoanilines of formula 1, in which case they constitute shading compositions which make it possible to give the hair extremely luminous glints and a pearly or iridescent appearance.

However, the hair-setting lotions of this invention can also contain other direct dyes, for example, anthraquinone dyes, nitro dyes of the benzene series, indamines, indophenols, oxazines, azines or indoanilines other than those of formula I.

The hair-setting lotions according to the invention are usually used by application to wet hair, previously washed and rinsed, followed by rolling the hair up on curlers and drying the hair.

The following examples are intended to illustrate the various aspects of the present invention. Unless otherwise specified, all parts and percentages are by weight and all temperatures are expressed in degrees Centigrade.

EXAMPLE 1 N-lZ'.4'-diamino) phenyll-3-methyl benzoquinone imine having the below formula is prepared as follows:

HEN o 1/2 11 0 CmHmNaO H2O Molecular weight found by potentiometric determination in dimethylformamide with 0.lN tetra-nbutylammonium hydroxide in solution in a mixture of isopropanol and methanol 234.

Analysis Calculated for Found m Ia n v1 2 C7r 66.10 66.26 6631 H7 5.93 6.01 5.91 N% 17.78 17.48 17.39

EXAMPLE 2.

N-[(2',4-diamino3',5'-dimethyl) phenyl]-3-methyl benzoquinone imine is prepared as follows CH3 NHQ CH3 There are dissolved, on the one hand, 0.01 mole (1.55 g) of 3-methyl quinone chloroimide in 25 cc of 96 ethanol and, on the other hand, 0.01 mole (2.09 g) of l,3-dimethyl-2,4-diamino benzene in 25 cc of water to which have been added 10 cc of ammonia at 22 Be and 1 cc of a normal soda solution. The two solutions, previously cooled, are mixed and the reaction mixture is allowed to stand for 20 minutes at 0C. The above indoaniline precipitates in the form of green crystals with golden glints. It is filtered, washed with ethyl alcohol and then with water. After vacuum drying, the product is chromatographically pure and melts at C.

Molecular weight calculated for C,,,H,,N ,O 255 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 258.

Analysis Calculated for Found CIHI7NIIO 5 C7: 70.59 70.49 70.42 H% 6.66 6.77 6.58 N% 16.47 16.28 16.26

EXAMPLE 3 N-[(3,5-dimethyl-2',4'-diamino) phenyl]-3,5- dimethyl benzoquinone imine, having the below formula, is prepared as follows:

1 5 CH NH CH N- -N: :01/2 0 H2 H2 CH3 CH3 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 275.

Analysis Calculated for Found dimethyl benzoquinone imine, having the below formula, is prepared as follows:

CH NH CH CH3 H N- N= =0 There are dissolved, on the one hand, 0.02 mole (3.4 g) of 2,3-dimethyl quinonechloroimide in 50 cc ofethyl alcohol and, on the other hand, 0.02 mole (4.18 g) of l,3-dimethyl-2,4-diamino benzene dihydrochloride in cc of water to which have been added 10 cc of ammonia at 22 Be and 5 cc ofa normal soda solution. The two solutions, previously cooled, are mixed and the reaction mixture is allowed to stand for an hour at ambient temperature, after which cc of ice water are added. Then 2.21 g of the above indoaniline are filtered which, after washing with water and vacuum drying, is chromatographically pure and melts at 206C.

Molecular weight calculated for 111 19N O. l/Z H O 27 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 284.

Analysis Calculated for Found CIGHIQNZIO 2 C7z 69.06 68.69 68.96 H'7r 7.19 7.03 7.12 N7( 15.10 15.00 15.11

EXAMPLE 5 N-[(2',4-diamino) phenyl]-2,5-dimethyl benzoquinone imine, having the below formula, is prepared as follows:

NR CH To a solution, cooled by an ice-salt mixture, of 0.02 mole (2.74 g) of 2,5-dimethyl-4-amino phenol and 0.02 mole (3.62 g) of metaphenylenediamine dihydrochloride in cc of 1.75 N soda solution there is added 0.02 mole (4.6 g) of ammonium persulfate in 50 cc of water to which have been added 15 cc of ammonia at 22 Be. The reaction mixture is allowed to stand for 45 minutes at 0C. The above indoaniline in crystal form is then filtered from the reaction mass and washed with water. After recrystallization in a dimethylformamidewater mixture and vacuum drying, the product melts at 173C.

Molecular weight calculated for C H, N -,O 241 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 243.

Analysis Calculated for Found u is a C'7r 69.70 69.2l 69.34 H71 622 6.18 625 N7: 17.42 l7.l4 l7.l7

EXAMPLE 6 N-[(3,5'-dimethyl-2',4'-diamino) phenyl]-2,5- dimethyl benzoquinone imine, having the below formula, is prepared in accordance with method 1, as follows:

To a solution of 0.015 mole (3.13 g) of 1,3-dimethy1- 2,4-diamino benzene dihydrochloride in 50 cc of ice water there are quickly added, first, 0.01 mole (2.3 g) of ammonium persulfate in 50 cc of ice water to which have been added 6 cc of ammonia at 22 Be, then, immediately afterward, 0.01 mole (1.37 g) of 2,5- dimethyl-4-amino phenol dissolved in 40 cc of 4N soda solution. The reaction mixture is allowed to stand for 10 minutes at C. The above indoaniline is filtered therefrom, washed with water and, after recrystallization in acetone, is in the form of green crystals with metallic glints and exhibiting a melting point of 207C.

Molecular weight calculated for C, H, N O 269 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 268.

dimethyl benzoquinone imine is prepared in accordance with method 2 as follows:

On the one hand, 0.01 mole (1.7 g) of 2,5-dimethyl quinonechloroimide is dissolved in 50 cc of 96 ethanol and, on the other hand, 0.01 mole (2.09 g) of 1,3- dimethyl-2,4-diamino benzene is dissolved in 25 cc of water to which have been added 10 cc of ammonia at 22 Be and 1 cc of normal soda solution. The two solutions, previously cooled, are mixed and the reaction mixture is allowed to stand for 30 minutes at 0C. The above indoaniline precipitates in the form of green crystals with metallic glints. It is filtered, washed with ethyl alcohol and then with water. The product, after vacuum drying, melts at 206C and does not show any drop in its melting point when mixed with the indoani line prepared according to example 6.

EXAMPLE 8 N[(2',4'-diamino) phenyl]-2-chloro benzoquinone imine, having the below formula, is prepared as follows:

C H N OCl 1/2 H O 256.5

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 254.

Analysis Calculated for Found C H N oCl A. H 0 C7: 56.14 55.91 55.84 H7z 4.67 4.59 461 N7: 16.37 16.54 16.43 Cl /z 13.84 13.61 13.78

EXAMPLE 9 N-[(2',4-diamino-5'-methoxy) phenyl]-2-chloro benzoquinone imine, having the below formula, is pre pared as follows:

NH Cl OCH A solution is prepared by dissolving 0.02 mole (3.60 g) of 2chloro-4-amino phenol hydrochloride in 50 cc of water. To this solution, cooled in an ice bath, there are added simultaneously, with stirring, with the aid of two dropping funnels, on the one hand, 0.02 mole (4.22 g) of 2,4-diamino anisole dihydrochloride dissolved in 50 cc of water, and, on the other hand, 0.02 mole (4.60 g) of ammonium persulfate dissolved in 50 cc of ice water to which have been added 50 cc of ammonia at 22 Be. The reaction mixture is allowed to stand for 15 minutes at 0C. The above indoaniline precipitates in crystallized form and is filtered therefrom. after which it is washed with water and vacuum dried. The product is chromatographically pure and melts at 197C.

Molecular weight calculated for C H N O Cl 277.5

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 272.

3,867,094 ll 12 EXAMPLE 10 after washing with water and vacuum drying, is chro- N-[(2,4'-diamino-5-methyl) phenyl]-2-chloro benmawgraph'cany Pure and melts zoquinone imine having thebelow formula is Prepared ig g Weight calculated for C"HN3CIO as follows: 5 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 278.

NH C1 Analysis Calculated for Found N 0 CHHHNKCIO C7: 60.98 60.78 61.14 14% 5.08 5.05 5.10 N71 15.24 15.27 15.02 cm 12.88 12.74 12.97

There are dissolved 0.02 mole (3.6 g) of 2-chloro-4- EXAMPLE 2 amino phenol hydrochloride and 0.02 mole (2.44 g) 2,4-diamino toluene in 100 cc of water. To this solu- N'l(2 'dlammo) phenyll'3'chloro benzoqumone tion, cooled to 0C, there is added little by little, with havmg the below formula is prepared as follows: stirring, 0.02 mole (4.6 g) of ammonium persulfate dissolved in 50 cc of water to which have been added cc of ammonia at 22 Be. The above indoaniline precipitates immediately in the form of mordore crystals. NH 1 The product is filtered washed with water and then 25 2 with isopropanol. After vacuum drying it is chromatographically pure and melts at 21 1C.

Molecular weight calculated for CmHmNgOCl HQN N 261.5

Molecular weight found by potentiometric determination in dimethylformamide with 0.1N tetra-nbutylammonium hydroxide in solution in a mixture of isopropanol and methanol 259. To a solution, cooled by an ice-salt mixture, of 0.02 mole (2.87 g) of 3-chloro-4-amino phenol and 0.02 3 mole (3.62 g) of metaphenylenediamine dihydrochloride in 70 cc of water to which have been added 50 cc Analysis Calculated for Found ofisopropanol, there is added 0.02 mole (4.6 g) of am- CV g mg n 59 43 59 37 monium persulfate in 50 cc of water to which have 7 5;, been added 25 cc of ammonia at 22 Be. The reaction N7( 16.06 15.88 15.93 mixture is allowed to stand for 15 minutes at 0C. The (1% 1.7.57 13.48 13.52

above indoaniline which has precipitated is filtered and washed with water. After recrystallization in a dimethylformamide-water mixture and vacuum drying, EXAMPLE 11 the product melts at 215C.

1 l phcnyll z chlom 24M(5)lCCUlal' weight calculated for C, H ,N OCI benzoquinone imine having the below formula is pre- Molecular welght found by potentiometnc determ1- pared as follows.

nation 1n d1methylformam1de w1th 0.1N tetra-nbutylammonium hydroxide in solution in a mixture of CH NH ()1 5O isopropanol and methanol 242 HQN N O 55 Analysis Calculated for I Found CH c% 58.18 57.95 57.87 H% 4.44 4.42 4.57 There are dlssolved 0.04 mole (7.20 g) of 2-chloro-4- 11% 16.97 16.62 16.83 amino phenol hydrochloride and 0.04 mole (8.36 g) l,3-dimethyl-2,4-diamino benzene dihydrochloride in 200 cc of water. To this solution, cooled to 0C, there is added little by little, with stirring, 0.04 mole (9.20 g) of ammonium persulfate dissolved in 100 cc of water to which have been added 50 cc of ammonia at 22 Be. EXAMPLE 13 The reaction mixture is allowed to stand for one hour N-l( m '-meth0xy) phenyll-3-chloro at 0C. The above indoaniline, which has precipitated benzoquinone imine, having the below formula, is prein the form of green crystals, is filtered. The product, pared as follows:

OCH

There are dissolved 0.03 mole (4.30 g) of 3-chloro-4- amino phenol and 0.03 mole of 2,4-diamino anisole dihydrochloride (6.33 g) in 250 cc of a 0.4N soda solution. To this solution, cooled to C, there is added, with stirring, 0.03 mole (6.9 g) of ammonium persulfate dissolved in 100 cc of water to which have been added 20 cc of ammonia at 22 Be. The above indoaniline which precipitates almost immediately is filtered, washed with water and recrystallized in a pyridinewater mixture. After vacuum drying, it melts at 218C.

Molecular weight calculated for C, H, N O Cl 277.5

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 273.

chloro benzoquinone imine, having the below formula, is prepared as follows:

NHGOCH C1 o To a solution of 0.015 mole (2.67 g) of 3- acetylamino-N,N-dimethylaniline in 25 cc of isopropanol, cooled in an ice-salt mixture, there are added simultaneously, with two dropping funnels, on the one hand, 0.01 mole (1.43 g) of 3-chloro-4-amino phenol in cc of isopropanol, and on the other hand, 0.012 mole (2.75 g) of ammonium persulfate in 35 cc of water to which have been added 6 cc ofammonia at 22 Be. The above indoaniline which immediately precipitates in the form of green crystals is filtered, washed with water and then with a 50% aqueous isopropanol solution. After vacuum drying the product melts at 198C.

Molecular weight C, H N O Cl=317.5

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 322.

calculated for EXAMPLE 15 NHGOCH C1 Nzz:

There are dissolved 0.01 mole (1.64 g) of 2-amino-4- acetylamino toluene and 0.01 mole (1.80 g) of 2- chloro-4-amino phenol hydrochloride in cc of water to which have been added 10 cc ofa normal HCl solution. To this resulting solution, previously cooled to 0C, are added, little by little, with stirring, 23 cc of a 28% ferric (,lllOI'ldG solution. When the addition is finished, the stirring is continued for 10 minutes. The above indoaniline hydrochloride precipitates and is filtered therefrom. After washing with water and with acetone and then vacuum drying, the product is chromatographically pure and melts with decomposition at 230C.

dimethyl benzoquinone imine described in Example 4, is prepared in accordance with method 2 as follows:

CH NR CH3 Step 1 Preparation of 2,3dimethyl benzoquinoneimine There are introduced 0.05 mole (6.85 g) of 2,3- dimethyl-4-amino phenol and 0.075 mole (17.4 g) of silver oxide and g of anhydrous sodium sulfate in 600 cc of anhydrous isopropyl ether. The resulting mixture is heated for four hours with reflux and stirring. The reaction mass is then filtered and the filtrate concentrated under vacuum to a volume of 10 cc. After cooling, cc of ligr'oin are added to the concentrated filtrate to precipitate 2,3-dimethyl benzoquinone imine, which is filtered and vacuum dried. There are obtained 5.5 g of this product which melts at 80C. Step 2 There are dissolved 0.003 mole (0.627 g) of 1,3- dimethyl-2,4-diamino benzene dihydrochloride in 10 cc of water to which has been added 1 cc of ammonia at 22 Be. To this solution, cooled in ice, there is added 0.002 mole (0.27 g) of the above 2,3-dimethyl benzoquinone monomine, dissolved at the moment of use in 5 cc of isopropanol. The above indoaniline, which precipitates, is filtered, washed with water and vacuum dried. The indoaniline melts at 206C and does not show any drop in its melting point when mixed with the product prepared according to Example 4.

EXAMPLE 17 The double chloride of zinc and N-[7'-(6-hydroxy- 4'-methyl-l '-oxa-4'-aza-1,2',3 ',4'-tetrahydro)-naph- Into cc of absolute ethyl alcohol there are introduced 0.01 mole (1.65 g) of 6-hydroxy-4-methyl phenomorpholine, 0.01 mole (1.51 g) of 2,5-dimethyl paranitrosophenol and 1.5 g of anhydrous zinc chloride. The reaction mixture is heated 45 minutes with reflux, with stirring. The reaction mass is then filtered hot to eliminate an insoluble light material. After cooling, 2.10 g of the double chloride of zinc and indoaniline are filtered which, after washing with alcohol and ethyl acetate, is chromatographically pure.

EXAMPLE l8 N-[(2',4'-diamino-6'-methyl) phenyl]-2,5-dimethyl benzoquinone imine, having the below formula, is prepared as follows:

There are dissolved 0.01 mole (1.37 g) of 2,5- dimethyl-4-amino phenol and 0.01 mole (1.95 g) of 3,5-diamino toluene dihydrochloride in 80 cc of 1.5N soda solution. To this solution, cooled in ice, there is added, little by little, with stirring, 0.01 mole (2.3 g) of ammonium persulfate dissolved in 50 cc of water. When the addition is finished, the stirring is continued I 10 minutes. The above indoaniline is filtered, washed with water and vacuum dried. The product is chromatographically pure and melts at 125C.

Molecular weight calculated for C H N O 255 Molecular weight found by potentiometric determination in methylisobutylketone by perchloric acid 258.

EXAMPLE 19 N-[(2,4'-diamino-5'-methoxy) phenyl]-2,6- dimethyl benzoquinoneimine, having the below formula, is prepared as follows:

NH CH3 H N- N 0 To a solution, cooled by an ice-salt mixture, of 0.01 mole (2.28 g) of ammonium persulfate in 30 cc of water there are added, first, 0.01 mole (2.1 l g) of 2,4- diamino anisole dihydrochloride in cc of water and then 30 cc of ammonia at 22 Be. Immediately thereafter, there is added 0.01 mole (1.91 g) of 2,6-dimethyl paraaminophenol monohydrate hydrochloride in solution in 50 cc of water. The reaction mixture immediately turns blue and and the above indoaniline rapidly crystallizes. The crude product is isolated by filtering. 1ts chromatogram reveals as an impurity a small amount of N-[(4'-hydroxy-3',5'-dimethyl) phenyl]- 2,6-dimethy1benzoquinoneimine resulting from the ox idizing condensation of 2,6-dimethyl paraaminophenol on it. After washing in iced acetone, 0.95 g of the pure product is obtained, which melts at 146C.

Molecular weight calculated for C H ;O N 271.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 266.

N-[(2,4-diamino-6'-methyl) phenyl]-2,6-dimethyl benzoquinoneimine, having the below formula, is prepared as follows:

H N N 0 CH3 CH To a solution, cooled by an ice-salt mixture, of 0.06 mole (13.68 g) of ammonium persulfate in 180 cc of water there are added, first, cc of ammonia at 22 Be, and then simultaneously, with two dropping funnels, on the one hand, 0.06 mole (11.7 g) of 3,5-

diamino toluene dihydrochloride in 260 cc of water and on the other hand, 0.06 mole (11.46 g) of 2,6- dimethyl paraaminophenol monohydrate hydrochloride in 600 cc of water. The reaction mixture rapidly takes on a blue coloring and the above indoaniline crystallizes after some minutes. It is isolated by filtering and thereafter washed with water and then with a little iced acetone to eliminate traces of N-[(4'-hydroxy-3',5'- dimethyl) phenyl-2,6-dimethyl benzoquinoneimine. The resulting product is chromatographically pure and melts at 171.

Molecular weight calculated for C H ON 256.

Molecular weight found by potentiometric determination in methylisobutylketone by perchloric acid 256.

N-[(2',4'-diamino-5'-methyl) phenyl]-2,6-dimethyl benzoquinoneimine, having the below formula, is prepared as follows:

To a solution, cooled by an ice-salt mixture, of 0.02 mole (4.56 g) of ammonium persulfate in 60 cc of water and 40 cc of ammonia at 22 Be, there are added simultaneously, with two dropping funnels, on the one hand, 0.02 mole (3.83 g) of 2,6-dimethyl paraaminophenol monohydrate hydrochloride in solution in 200 cc of water and, on the other hand, 0.02 mole (2.44 g) of metatoluylenediamine solution in 25 cc of acetone. The reaction mixture rapidly takes on a blue shade and the above indoaniline crystallizes. It is isolated by filtering, washed with water and vacuum dried. The product is chromatographically pure and melts at 1 13 C.

Molecular weight calculated for C H O N 255.

Molecular weight found by potentiometric determination in methylisobutylketone by perchloric acid 260.

dimethyl benzoquinoneimine, having the below formula, is prepared in accordance with method 1 as follows:

CH3 NH CH To a solution, cooled with an ice-salt mixture, of 0.04 mole (9.12 g) of ammonium persulfate in 120 cc of water and cc of ammonia at 22 Be, there are added simultaneously and rapidly, with two dropping funnels, on the one hand, 0.04 mole (7.66 g) of 2,6-dimethyl paraaminophenol monohydrate hydrochloride in solution in 400 cc of water and, on the other hand, 0.04 mole (8.36 g) of l,3-dimethyl-2,4-diamino benzene dihydrochloride in solution in 200 cc of water. The reaction mixture immediately turns blue and the above indoaniline crystallizes. The crystallized product is filtered, washed with ice water and then with iced acetone and vacuum dried. 3.6 g of chromatographically pure product is obtained which melts at 196.

Molecualr weight calculated for C H O N 269 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 269.

Analysis Calculated for Found CIEHIQO il C7r 71.37 70.46 70.68 H71 7.06 7.05 7.03 N71 15.61 15.48 15.37

EXAMPLE 231 To a solution of 0.04 mole (6.38 g) of 2-methy1 paraaminophenol hydrochloride and 0.04 mole (8.36 g) of l,3-dimethyl-2,4-diamino benzene dihydrochloride in 320 cc of a 0.4 N soda solution there is added, with stirring, 0.04 mole (9.12 g) of ammonium persul fate in cc of water, while cooling the reaction mixture with an ice-salt mixture. The above indoaniline crystallizes immediately. The crystallized product is filtered and washed with water. After recrystallization in an acetone-water mixture, it melts at 123.

Molecular weight calculated for c,,u,,o N 255.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 249.

dimethyl benzoquinoneimine, having the formula below, is prepared as follows:

To a solution, cooled by an ice-salt mixture, of 0.02 mole (4.6 g) of ammonium persulfate in 606 cc of water and 50 cc of ammonia at 22 Be, there are added simultaneously and rapidly, with two dropping funnels, on the one hand, 0.02 mole (3.83 g) of 2,6-dimethyl paraaminophenol monohydrate hydrochloride in 200 cc of water and, on the other hand, 0.02 mole (4.18 g) of N,N-dimethylmetaphenylenediamine dihydrochloride in 100 cc of water. The reaction mixture instantly turns blue and the above indoaniline precipitates in crystallized form. The crude product is filtered, washed with water and then with iced acetone to eliminate traces of N-[(4-hydroxy-3,5-dimethyl) phenyl]-2,6- dimethyl benzoquinoneimine. After recrystallization in a pyridine-water mixture and vacuum drying, the product melts at 240.

Molecular weight calculated for C, H, N O 269.

"Molecular weight found by potentiometric determination in acetic acid by perchloric acid 264.

The double chloride of zinc and N[7'-(6'-hydroxy- 4'-methyl-l'oxa-4'-aza-1,2',3',4'-tetrahydro)- naphthyl]2,6-dimethyl benzoquinoneimine having the below formula, is prepared as follows:

In 12 cc of absolute ethyl alcohol, to which have been added two drops of hydrochloric acid (d= 1.18) there are introduced 0.01 mole (1.65 g) of 6-hydroxy-4- methyl phenomorpholine, 0.01 mole (1.51 g) of 2,6- dimethyl paranitrosophenol and 1.5 g of anhydrous zinc chloride. The reaction mixture is heated for 30 minutes with reflux. After cooling, there are filtered therefrom, in the form of green crystals, 1.9 g of double chloride of zinc and the above indoaniline which, after washing with 50 ethyl alcohol, is chromatographically pure.

EXAMPLE 26 N-[7'-(6'-hydroxy-l'-oxa-4'-aza-1',2',3',4'- tetrahydro-naphthyll-2-methyl benzoquinoneimine monohydrate, having the below formula, is prepared as follows:

OH OH There are dissolved 0.004 mole (0.604 g) of 6- hydroxy phenomorpholine and 0.004 mole (0.637 g) of 2-methyl-4-amino phenol hydrochloride in 400 cc of 0.025 N soda solution. Air is bubbled for three hours into the reaction mixture which progressively takes on a green coloring. 0.460 g of crystallized indoaniline is filtered which, after washing with water and vacuum drying, melts at 298.

Analysis Calculated for Found C, H O N,.H O C% 62.50 62.23 62.32 H% 5 .56 5.75 5.64 N% 9.72 9.80 9.95

EXAMPLE 27 N-[(2,4-diamino) phenyl]-2,6-dimethyl benzoquinoneimine, having the formula below, is prepared as follows:

(7.24 g) of metaphenylenediamine dihydrochloride. The reactionmixture immediately takes on a blue coloring and the above indoaniline precipitates in crystallized form. It is filtered, washed with water and then with acetone. After vacuum drying, the product melts at 162.

Molecular weight calculated for C H N O 241 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 243.

below formula, is prepared as follows:

NHCOCH CH 1) N N CH3 There are dissolved, on the one hand, 0.01 mole (1.91 g) of 2,6-dimethyl paraaminophenol monohydrate hydrochloride and on the other hand, 0.0125 mole (2.22 g) of N,N-3-dimethylamino acetanilide in 100 cc of water, 20 cc of isopropanol and 5 cc of ammonia at 22 Be. To this resulting solution, cooled with an ice-salt mixture, there is added little by little, with stirring, 0.02 mole of potassium ferricyanide in solution in 30 cc of water. When the addition is finished, stirring is continued for 30 minutes. 300 cc of ice water is then added to the reaction mixture. 1.15 g of the above indoaniline are recovered by filtration. After washing with water and acetone, the product is chromatographically pure and melts at 237.

Molecular weight calculated for C, H ,O N 31 1.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 304.

EXAMPLE 29 N-[(2,4'-diamino-5'-methoxy) phenyl)-2-methyl benzoquinoneimine, having the below formula, is prepared as follows:

There is dissolved 0.05 mole (6.15 g) of 2-methyl-4- amino phenol in 100 cc of 0.5 N soda solution. To this solution there are added 0.05 mole (11.4 g) of ammonium persulfate in cc of water, to which have been added 15 cc of ammonia at 22 Be and 0.05 mole (10.55 g) of 2,4-diamino anisole dihydrochloride in solution in 250 cc of water to which have been added 5 cc of ammonia at 22 Be, while keeping the temperature of the reaction mixture in the vicinity of 0C. The above indoaniline precipitates in crystallized form. It is filtered, washed with water and vacuum dried. The product is chromatographically pure and melts at Analysis Calculated for Found i-i is z a C% 65.37 65.19 65.03 H% 5.83 5.85 6.00 N% 16.33 16.35 16.22

EXAMPLE 30 N-[(6'-amino-l '-oxa-4'-aza-1',2,3',4-tetrahydro 7'-naphthyl]-2-methyl benzoquinoneimine, having the below formula, is prepared as follows:

NH2 033 M "G 0.02 mole (3.19 g) of 2-methyl-4-amino phenol hydrochloride and 0.02 mole (4.46 g of 6-amino phenomorpholine are dissolved in 280 cc of 0.25 N soda solution. Air isbubbled in this solution for three hours.

40 Then acetic acid is added to the reaction mixture until a pH equal to 8.5 is obtained. The above indoaniline which precipitates is filtered in crystallized form. After washing with water and vacuum drying, the product is chromatographically pure and melts at 288.

Molecular weight calculated for C I-1 0 19 269. Molecular weight found by potentiometric determination in acetic acid by perchloric acid 264.

mula, is prepared in accordance with method 2 as follOWSI 3 2 0.003 mole (0.627 g) of l,3-dimethyl-2,4-diamino benzene dihydrochloride is dissolved in ll cc of 0.82 N soda solution. To this solution, cooled to there is added 0.002 mole (0.339 g) of 2,6-dimethyl-N- chlorobenzoquinone monoimine in solution in 6 cc of isopropanol. The reaction mixture rapidly turns blue. It is allowed to stand for one hour at 0. Then 0.400 g of the above indoaniline is isolated in the form of beautiful green flakes with golden glints by filtering. After washing with water and extended vacuum drying, the product melts at 196 (no drop of melting point is observed when used in mixture with the product prepared according to Example 22).

Molecular weight calculated for C H O N 269.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 272.

EXAMPLE 32 CH NR .HEN-

0.003 mole (0.627 g) of l,3-dimethyl-2,4-diamino benzene dihydrochloride is dissolved in 10 cc of water to which has been added 1 cc of ammonia at 22 Be. To this solution, cooled to 0C, there is added 0.003 mole (0.405 g) of 2,6-dimethyl benzoquinone monoimine in 5 cc of isopropanol. The reaction mixture immediately takes on a blue coloring and the above indoaniline precipitates in a few seconds in the form of green-mordore crystals. The indoaniline is filtered, washed with distilled water and vacuum dried. There is obtained 0.24 g of chromatographically pure product, which melts at 196 (no drop in melting point when used with the product prepared according to Example 22 is observed).

Molecular weight calculated for C l-l O N 269.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 268.

EXAMPLE 33 The following hair-setting lotion composition is prepared:

Dye of Example I 0.05 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. for 50 Water, q.s.p. I00 g Triethanolamine, q.s.p. pH 7 24 This hair-setting lotion composition when applied to bleached hair, imparts thereto a parme shade with pearly glints EXAMPLE 34 The following hair-setting lotion composition is prepared:

Dye of Example 2 0.025 g Vinyl acetate-crotonic acid copolymer (vinyl acetate crotonic acid l0%,

molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. X00 g Ammonia, at 22 Be, q.s.p. pH 6 This hair-setting lotion when applied to bleached hair, imparts thereto a pearly pale mauve shade.

EXAMPLE 35 The following dye composition is prepared:

Dye of Example 2 O.l0 g Ethyl alcohol, 96 titer, q.s.p. 60 Water, q.s.p. I00 g The final pH of the solution is 8.5.

This dye composition when applied for 20 minutes, at ambient temperature, to white hair, imparts thereto, after rinsing and shampooing, a mauve shade.

EXAMPLE 36 g The following dye composition is prepared:

Dye of Example 3 0.4 g Ethyl alcohol, 96 titer 40 g Water, q.s.p. 100 g l% lactic acid, q.s.p. pH 5 This dye composition when applied to 95% naturally white hair for 20 minutes at ambient temperature, imparts thereto after rinsing and shampooing an ash beige color with violet glints.

EXAMPLE 37 The following dye composition solution is prepared:

parts thereto after rinsing and shampooing, a very luminous intense violet shade.

EXAMPLE 38 The following hair-setting lotion composition is prepared:

Dye of Example 5 0.005 g Vinyl acetate-crotonic acid copolymer (vinyl acetate, 90% crotonic acid,

10%, molecular weight 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. I00 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a pearly appearance with almond green glints.

EXAMPLE 39 The following hair-setting lotion is prepared:

Triethanolarnine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a silvery gray shade with iridescent glints.

EXAMPLE 40 The following hair-setting lotion composition is prepared:

Dye of Example 6 0.025 g Vinyl acetatecrotonic acid copolymer (vinyl acetate 90%, crotonic acid molecular weight 45,000 50,000) 2 g Ethyl alcohol, 96 titer, g.s.p. 50 Water, g.s.p. 100 g Ammonia, 22 Be, q.s.p. pH 8 This hair-setting lotion when applied to bleached hair, imparts thereto a silvery pale mauve shade.

EXAMPLE 41 The following hairsetting lotion is prepared:

Dye of Example 6 0.05 g N-l(2,4"diamino-5'-methoxyl phenyl] benzoquinoneimine 0.025 Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid [071, molecular weight 45,000 50.000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine. qsp. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a silvery blue gray shade.

EXAMPLE 42 The following hair-setting lotion is prepared:

Dye of Example 8 Vinyl acetate-crotonlc acid copolymer (vinyl acetate 90%, crotonic acid a 10%. molecular weight 45,000 to 50,000) Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair imparts thereto an intense gray blue shade.

EXAMPLE 43 The following hair-setting lotion is prepared:

Dye of Example 9 Vinyl acetate-crotonic acid copolymer (vinyl (acetate 90%, crotonic acid 10%,

-Continued molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a pearly ash beige shade.

EXAMPLE 44 The following dye composition is prepared:

Dye of Example 9 Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide Water, q.s.p.

Ammonia, at 22 Be, q.s.p pH 8.5

This dye composition when applied to 95% naturally white hair, for 15 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a coppery blond shade.

EXAMPLE 45 The following hair-setting lotion is prepared:

Dye of Example 10 Vinyl acetate-crotonic acid copolymer (vinyl acetate crotonic acid 107:, molecular weight, 45,000 50.000)

Ethyl alcohol, 96 titer. q.s.p. 50

Water, q.s.p.

Ammonia, at 22 Be, q.s.p. pH 8 This hair-setting lotion when applied to bleached hair, imparts thereto a silvery mauve gray shade.

EXAMPLE 46 The following dye composition is prepared:

Dye of Example 11 0.1 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. 100 g Ammonia, at 22 Be. q,s.p. pH 10 This dye composition when applied to naturally white hair for 20 minutes at ambient temperature, imparts, after rinsing and shampooing, a silvery gray shade.

EXAMPLE 47 The following hair-setting lotion is prepared:

Dye of Example 12 0.025 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight,

45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50" Water, q.s.p. 100 g Tricthanolamine, q.sp. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a pearly appearance with mauve glints.

EXAMPLE 4% The following hair-setting lotion is prepared:

Dye of Example 13 0.05 g

-Continued Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid l%, molecular weight,

45,000 50,000) l g Ethyl alcohol, 96 titer, q.s.p. 25 Water, q.s.p. 100 g l% lactic acidsolution, q.s.p. pH

This hair-setting lotion when applied to bleached hair, imparts thereto an intense pearly pink shade.

EXAMPLE 49 The following dye composition is prepared:

Dye of Example 14 0.2 g Ethyl alcohol, 96 titer, q.s.p: 65 Water, q.s.p. 100 g 1% lactic acid, q.s.p. pH 5.5

This dye composition when applied to 95% naturally white hair for 25 minutes at 35, imparts thereto after rinsing and shampooing a light pearly green shade.

EXAMPLE 50 The following dye composition is prepared:

Dye of Example l3 0.2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. l00 g Ammonia, at 22 Be, q.s.p. pH

This dye composition when applied to 95% naturally white hair for minutes at ambient temperature, imparts thereto after rinsing and shampooing, a luminous beige with light pink glints.

EXAMPLE 51 The following hair-setting lotion is prepared:

Dye of Example 15 0.05 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. I00 g Triethanolamine, q.s.p. pH 5.5

This hair-setting lotion when applied to bleached hair imparts thereto, a very luminous, pearly blue green shade.

EXAMPLE 52 The following dye composition is prepared:

2,6-dimethyl benzoquinone imine 0.l g Ethyl alcohol, 96 titer 30 g Water, qsp. I00 g Ammonia, at 22 Be, q.s.pv pH l0 This dye composition when applied to bleached hair for 10 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a silvery gray shade with rose glints.

EXAMPLE 53 The following hair-setting lotion is prepared:

Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair imparts thereto, a bluish silvery gray shade.

EXAMPLE 54 The following hair-setting lotion is prepared:

Dye of Example 17 0.05 g Vinyl acetate crotonic acid polymer (vinyl acetate crotonic acid 10%, molecular weight, 45,000 50.000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.sip. I00 g Triethanolamine, q.s.p: pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a light rose beige shade with silvery glints.

EXAMPLE 55 The following dye composition is prepared:

Dye of Example 16 Nitroparaphenylenediamine Butylglycol Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide Water, q.s.p.

Ammonia, at 22 Be, q.s.p. pH 6 This dye composition when applied to naturally white hair, for 10 minutes at ambient temperature, imparts thereto after rinsing and shampooing, a violet coloring.

EXAMPLE 56 The following hair-setting lotion is prepared:

Dye according to Example l9 0.] g Vinyl acetate-crotonic acid compolymer (vinyl acetate 90%, crotonic acid 10%, average molecular weight, 45,000

50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a pearly rose beige shade.

EXAMPLE 57 The following dye composition is prepared:

Dye according to Example l9 0.4 g Ethyl alcohol, 96 titer 40 g Water, q.s.p. 100 g Ammonia, at 22Be, q.s.p. pH l0 This dye composition when applied to 95% naturally white hair for 20 minutes at ambient temperature, imparts thereto after rinsing and shampooing, a silvery gray shade with rose glints.

EXAMPLE 58 The following hair-setting lotion is prepared:

Dye according to Example 20 Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, average molecular weight 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50

Water, q.s.p.

Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached 10 hair, imparts thereto a pearly pale green shade.

EXAMPLE 59 The following dye composition is prepared:

Dye according to Example 21 0.3 g Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles ethylene oxide 5 g Water, q.s.p. 100 g The pH is equal to 7.

This dye composition when applied to 95% naturally white hair for 15 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a silvery gray shade with violet glints.

EXAMPLE 60 The. following dye composition is prepared:

Dye according to Example 23 0.25 g Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide 5 g Water, q.s.p. 100

The pH is equal to 7.

This dye composition when applied to 60% naturally white hair, for 20 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a deep purplish violet shade.

EXAMPLE 61 The following hair-setting lotion is prepared:

Dye of Example 23 Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight, 45,000 50,000)

Ethyl alcohol, 96 titer, q.s.p.

Water, q.s.p.

Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto, a very luminous mauve shade.

Ammonia, at 22 Be; q.s.p. pH 10 This composition when applied to 95% naturally white hair, for 10 minutes at ambient temperature, imparts -thereto, after rinsing and shampooing, a pearly violet beige shade.

EXAMPLE 63 The following dye composition is prepared:

Dye of Example 23 0.05 g Ethyl alcohol, 96titer 20 g Water, q.s.p. 100 g 10% lactic acid, q.s.p. pH 4.5

This dye composition when applied to 95% naturally white hair, for 10 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a pearly rose beige shade.

EXAMPLE 64 The following dye composition is prepared:

Dye of Example 23 Water q.s.p. Ammonia at 10%, q.s.p. pH 10 Thisdye composition when applied to bleached hair for 10 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a very luminous pale rose blond shade.

EXAMPLE 65 The following hair-setting lotion is prepared:

Dye of Example 25 0.05 g Vinyl acetate-crotonic acid copolymer (vinyl acetate crotonic acid 10%, molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p, 100 g Triethanolaminc, q.s.p. pH 7 This hair-setting when applied to bleached hair, imparts thereto, a rose shade with golden glints.

EXAMPLE 66 The following dye composition is prepared:

Dye of Example 25 0.4 g Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide 5 g Water, q.s.p. 100 g The pH is equal to 7.

This dye composition when applied to white hair, for 20 minutes at ambient temperature, imparts thereto, after rinsing and shampooing, a very luminous golden blond shade with rose glints.

EXAMPLE 67 The following hair-setting lotion is prepared:

Dye of Example 26 0.15 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. I00 g Triethanolamine, q.s.p. pH 7 This hairsetting lotion when applied to bleached hair, imparts thereto, a pearly pale almond green shade.

Triethanolamine, q.s.p. pH 7 This hair setting lotion when applied to bleached hair, imparts thereto, a rose shade with golden glints.

EXAMPLE 69 The following hair-setting lotion is prepared:

Dye of Example 29 0.005 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair imparts thereto, a light blond shade that is slightly rose.

EXAMPLE 70 The following hair-setting lotion is prepared:

Dye of Example 30 0.05 g Crotonic acid-vinyl acetate copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Tricthanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair imparts thereto, a violet rose shade.

EXAMPLE 71 The following hair-setting lotion is prepared: 8n

Dye of Example 28 0.15 g

Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%, molecular weight, 45,000 50,000)

Ethyl alcohol, 96 titer, q.s.p. 50

Water, q.s.p.

Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto, a strongly silvered, pale blue shade.

EXAMPLE 72 The following dye composition is prepared:

Dye of Example 22 0.05 g Ethyl alcohol, 96 titer 25 g Water, q.s.p. 100 g The pH of the dye composition is equal to 7.

This dye composition when applied to bleached hair imparts thereto, after a minute contact period and after rinsing and shampooing, a slightly mauve silvery gray shade.

EXAMPLE 73 The following dye composition isprepared:

Dye of Example 22 0.1 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. 100 g 10% lactic acid, q.s.p. pH 5 This dye composition when appliedto 95% naturally white hair, imparts thereto, after a 10 minute contact period and after rinsing and shampooing, a pearly beige gray shade.

EXAMPLE74 The following hair-setting lotion is prepared:

Dye of Example 27 0.03 g Vinyl acetate-crotonic acid copolymer (vinyl acetate crotonic acid 10%, molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto, a very luminous green blue shade.

EXAMPLE 75 The following hair-setting lotion is prepared:

Dye of Example 24 0.05 g Vinyl acetate-crotonic acid copolymer (as in Example 74) 2 g Ethyl alcohol, 96" titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto, a pearly green blue shade.

EXAMPLE 76 The following dye composition is prepared:

Dye of Example 29 0.15 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Ammonia, at 22 Be, q.s.p. pH 10 This dye composition when applied for 20 minutes to naturally white hair, imparts thereto, after rinsing and shampooing a violet shade.

EXAMPLE 77 The following dye composition is prepared:

Dye of Example 19 0.2 g N-[(4'-hydroxy) phenyl]-2,6-dimethyl benzoquinone imine 0.1 g Ethyl alcohol, 96 titer 25 g Water, q.s.p. 100 g Ammonia, at 22 Be, q.s.p. pH 10 This dye composition when applied for 20 minutes to 95% naturally white hair, imparts thereto, after rinsing and shampooing, an ash dark gray shade with violet glints.

EXAMPLE 78 The following dye composition is prepared:

Ammonia, at 22 Be, q.s.p. pH 9 This dye composition when applied for 15 minutes to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a golden green shade.

l EXAMPLE 79 The following hair-setting lotion is prepared:

Dye of Example 25 0.05 g N-l(4'-dimethylamino) phenyl]-2,5-dimethyl benzoquinoneimine 0.05 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90%, crotonic acid 10%. molecular weight, 45,000 50,000) 2 g Ethyl alcohol, 96 titer, q.s.p. 50 Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto, a silvery mauve shade.

What is claimed is: 1. A dye composition for keratinous fibers comprising an aqueous solution of an indoaniline selected from the group consisting of a. an indoaniline having the formula R 2 R R R6 R7 R3 Ru wherein R R R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-6 carbon atoms and halogen with the proviso that l-2 of R R R and R are other than hydrogen; R R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having l-6 carbon atoms and lower alkoxy having l-6 carbon atoms; R represents a member selected from the group consisting of hydrogen and lower alkyl having l-6 carbon atoms; R represents a member selected from the group consisting of hydrogen and lower alkyl having l-6 carbon atoms and together with R and the nitrogen atom to which R is attached form dihiydro-oxazine; and Z represents a member selected from the group consisting of amino, acetylamino and hy'droxy,

b. the hydrochloride of said indoaniline in (a) and c. a double chloride of zinc and said indoaniline in (a), said indoaniline being present in amounts of 0.002-2 percent by weight of said composition.

2. The dye composition of claim 1 having a pH ranging between 4 11.

3. The dye composition of claim 1 which also contains a low molecular weight alkanol present in amounts of 20 weight percent of said composition.

4. The dye composition of claim 3 wherein said low molecular weight alkanol is selected from the group consisting of ethanol and isopropanol.

5. The dye composition of claim 1 which also includes a glycol selected from the: group consisting of propylene glycol and butyl glycol present in amounts of l-6 weight percent of said composition.

6. The dye composition of claim 1 also including a dye selected from the group consisting of a nitrobenzene dye, an indophenoland an indoaniline other than that defined in claim 1.

7. A process of dyeing keratinous fibers, comprising impregnating said fibers to be dyed with the composition of claim 1 in amounts effective to dye said keratinous fibers, permitting said composition to remain in contact with said fibers for a period ranging from about 3 to 30 minutes, rinsing said fibers and drying said fibets.

8. The composition of claim 1 wherein (l) the aqueous solution comprises an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol present in amounts of about 20 to 70 percent by weight of said composition (2) said composition also includes l-3 percent by weight of a film forming resin selected from the group consisting of pol yvinylpyrrolidone having a molecular weight of 10,000-400,000, copolymer of 10% crotonic acid and vinyl acetate having a molecular weight ranging from 10,000 to 70,000 and a copolymer of vinylpyrrolidone and vinyl acetate having a molecular weight ranging from about 30,000 to 200,000 wherein the ratio of VP to VA ranges between 50-70150-30, and (3) said indoaniline is present in amounts of about 0.002 to 1 percent by weight of said composition. 

2. The dye composition of claim 1 having a pH ranging between 4 -
 11. 3. The dye composition of claim 1 which also contains a low molecular weight alkanol present in amounts of 20 - 70 weight percent of said composition.
 4. The dye composition of claim 3 wherein said low molecular weight alkanol is selected from the group consisting of ethanol and isopropanol.
 5. The dye composition of claim 1 which also includes a glycol selected from the group consisting of propylene glycol and butyl glycol present in amounts of 1-6 weight percent of said composition.
 6. The dye composition of claim 1 also including a dye selected from the group consisting of a nitrobenzene dye, an indophenol and an indoaniline other than that defined in claim
 1. 7. A process of dyeing keratinous fibers, comprising impregnating said fibers to be dyed with the composition of claim 1 in amounts effective to dye said keratinous fibers, permitting said composition to remain in contact with said fibers for a period ranging from about 3 to 30 minutes, rinsing said fibers and drying said fibers.
 8. The composition of claim 1 wherein (1) the aqueous solution comprises an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol present in amounts of about 20 to 70 percent by weight of said composition (2) said composition also includes 1-3 percent by weight of a film forming resin selected from the group consisting of polyvinylpyrrolidone having a molecular weight of 40,000-400,000, copolymer of 10% crotonic acid and 90% vinyl acetate having a molecular weight ranging from 10,000 to 70,000 and a copolymer of vinylpyrrolidone and vinyl acetate having a molecular weight ranging from about 30,000 to 200,000 wherein the ratio of VP to VA ranges between 50-70:50-30, and (3) said indoaniline is present in amounts of about 0.002 to 1 percent by weight of said composition. 